A computational study of aromaticity and photophysical properties of unsymmetrical azatrioxa[8]circulenes

Gleb V. Baryshnikov, Rashid R. Valiev, Boris F. Minaev, Hans Ågren

Research output: Contribution to journalArticle

8 Citations (Scopus)

Abstract

Owing to their potential use in organic light-emitting diodes and field-effect transistors we present a theoretical study of a series of unsymmetrical azatrioxa[8]circulenes in order to explain the impact of outer substituents and benzoannelation on photophysical constants and aromaticity of these compounds in terms of spin-orbit coupling perturbation and magnetically-induced ring currents. It is argued that the S1-Tn inter-system crossing processes constitute the main deactivation pathways for the fluorescence quenching, something that is supported by a good agreement obtained with experimental data on fluorescence quantum yields. The concept of the gauge-including magnetically induced currents has been applied in order to estimate the role of substituents and benzoannelated fragments on the aromaticity and particularly on the overall balance between the diatropic “aromatic” and paratropic “antiaromatic” current strengths. While a variation of the substituents in the outer perimeter of the studied circulenes does not provide a clear effect on their aromaticity, it is demonstrated that an additional benzoannelation (π-extension) of the azatrioxa[8]circulene macrocycle induces a significant aromaticity enhancement.

Original languageEnglish
Pages (from-to)2717-2723
Number of pages7
JournalNew Journal of Chemistry
Volume41
Issue number7
DOIs
Publication statusPublished - 2017

Fingerprint

Fluorescence
Induced currents
Organic light emitting diodes (OLED)
Quantum yield
Field effect transistors
Gages
Quenching
Orbits

ASJC Scopus subject areas

  • Catalysis
  • Chemistry(all)
  • Materials Chemistry

Cite this

A computational study of aromaticity and photophysical properties of unsymmetrical azatrioxa[8]circulenes. / Baryshnikov, Gleb V.; Valiev, Rashid R.; Minaev, Boris F.; Ågren, Hans.

In: New Journal of Chemistry, Vol. 41, No. 7, 2017, p. 2717-2723.

Research output: Contribution to journalArticle

Baryshnikov, Gleb V. ; Valiev, Rashid R. ; Minaev, Boris F. ; Ågren, Hans. / A computational study of aromaticity and photophysical properties of unsymmetrical azatrioxa[8]circulenes. In: New Journal of Chemistry. 2017 ; Vol. 41, No. 7. pp. 2717-2723.
@article{a195a3b050d54188a82e36efebd1b2a3,
title = "A computational study of aromaticity and photophysical properties of unsymmetrical azatrioxa[8]circulenes",
abstract = "Owing to their potential use in organic light-emitting diodes and field-effect transistors we present a theoretical study of a series of unsymmetrical azatrioxa[8]circulenes in order to explain the impact of outer substituents and benzoannelation on photophysical constants and aromaticity of these compounds in terms of spin-orbit coupling perturbation and magnetically-induced ring currents. It is argued that the S1-Tn inter-system crossing processes constitute the main deactivation pathways for the fluorescence quenching, something that is supported by a good agreement obtained with experimental data on fluorescence quantum yields. The concept of the gauge-including magnetically induced currents has been applied in order to estimate the role of substituents and benzoannelated fragments on the aromaticity and particularly on the overall balance between the diatropic “aromatic” and paratropic “antiaromatic” current strengths. While a variation of the substituents in the outer perimeter of the studied circulenes does not provide a clear effect on their aromaticity, it is demonstrated that an additional benzoannelation (π-extension) of the azatrioxa[8]circulene macrocycle induces a significant aromaticity enhancement.",
author = "Baryshnikov, {Gleb V.} and Valiev, {Rashid R.} and Minaev, {Boris F.} and Hans {\AA}gren",
year = "2017",
doi = "10.1039/c6nj03925a",
language = "English",
volume = "41",
pages = "2717--2723",
journal = "New Journal of Chemistry",
issn = "1144-0546",
publisher = "Royal Society of Chemistry",
number = "7",

}

TY - JOUR

T1 - A computational study of aromaticity and photophysical properties of unsymmetrical azatrioxa[8]circulenes

AU - Baryshnikov, Gleb V.

AU - Valiev, Rashid R.

AU - Minaev, Boris F.

AU - Ågren, Hans

PY - 2017

Y1 - 2017

N2 - Owing to their potential use in organic light-emitting diodes and field-effect transistors we present a theoretical study of a series of unsymmetrical azatrioxa[8]circulenes in order to explain the impact of outer substituents and benzoannelation on photophysical constants and aromaticity of these compounds in terms of spin-orbit coupling perturbation and magnetically-induced ring currents. It is argued that the S1-Tn inter-system crossing processes constitute the main deactivation pathways for the fluorescence quenching, something that is supported by a good agreement obtained with experimental data on fluorescence quantum yields. The concept of the gauge-including magnetically induced currents has been applied in order to estimate the role of substituents and benzoannelated fragments on the aromaticity and particularly on the overall balance between the diatropic “aromatic” and paratropic “antiaromatic” current strengths. While a variation of the substituents in the outer perimeter of the studied circulenes does not provide a clear effect on their aromaticity, it is demonstrated that an additional benzoannelation (π-extension) of the azatrioxa[8]circulene macrocycle induces a significant aromaticity enhancement.

AB - Owing to their potential use in organic light-emitting diodes and field-effect transistors we present a theoretical study of a series of unsymmetrical azatrioxa[8]circulenes in order to explain the impact of outer substituents and benzoannelation on photophysical constants and aromaticity of these compounds in terms of spin-orbit coupling perturbation and magnetically-induced ring currents. It is argued that the S1-Tn inter-system crossing processes constitute the main deactivation pathways for the fluorescence quenching, something that is supported by a good agreement obtained with experimental data on fluorescence quantum yields. The concept of the gauge-including magnetically induced currents has been applied in order to estimate the role of substituents and benzoannelated fragments on the aromaticity and particularly on the overall balance between the diatropic “aromatic” and paratropic “antiaromatic” current strengths. While a variation of the substituents in the outer perimeter of the studied circulenes does not provide a clear effect on their aromaticity, it is demonstrated that an additional benzoannelation (π-extension) of the azatrioxa[8]circulene macrocycle induces a significant aromaticity enhancement.

UR - http://www.scopus.com/inward/record.url?scp=85016316941&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=85016316941&partnerID=8YFLogxK

U2 - 10.1039/c6nj03925a

DO - 10.1039/c6nj03925a

M3 - Article

VL - 41

SP - 2717

EP - 2723

JO - New Journal of Chemistry

JF - New Journal of Chemistry

SN - 1144-0546

IS - 7

ER -